Halogenated arobiatic compounds



Patented Aug. 14, 1951 2,564,214 HALOGENATED ABOMATJC COMPOUNDS Sidney D. Ross and Moushgy Markuzriam, North Adams, Mass, ass'ignors to iSprme Electric Company, North Adams, Mass. a corporation of Massachusetts No Drawing. Application February 28, 1948, vSerial No. 12,138

This invention relates to a new group of halogenated ethers. More particularly it refers to certain dialkyl others in which one of the alkyl groups is substituted with a halogenated aromatic nucleus.

It is an object of this invention to produce new and useful compounds possessing high boiling points and unusual chemical stability. A further object is to produce valuable polar dielectric compositions. Another object is to provide new and useful, flame-resistant, pentachlorobenzyl alkyl 'ethers. Additional objects will become apparent from a consideration of the following description and claim.

The compounds of our invention conform to the general formula:

in which R represents a bivalent, saturated, aliphatic hydrocarbon radical, 13. represents a mono valent aliphatic hydrocarbon radical, and n represents an integer from 1 .to 2.

In a more limited sense the invention is concerned with compounds conforming to the general formula:

onion).

t-n in which R and 11. have the same significance as above.

:Still more specifically the invention pertains to compounds conforming to the general formula:

C1- CH OR in which R represents an alkyl group.

The preferred compounds of the invention, which conform to the last formula given above. are pentachlorobenzyl alkyl ethers. Among the preferred alkyl ethers of this type are Pentachlorobenzyl methyl ether Pentachlorobenzyl ethyl ether Pentachlorobenzyl n-propyl ether Pentachlorobenzyl isopropyl ether Pentachlorobenzyl butyl ether Pentachlorobenzyl amyl ether 1 Claim. (Cl. 260-611) Other compounds of the invention, which conform to the first general formula when the integer n is 2, are also :of particular interest. Among the preferred compounds of this series are 1:2 'bisipropoxymethyl) -3.,4,5, 6 tetrachloroben- ZED-B 1,4 his-(propoxymethyl) 23,5,6-tetrach1or0behm 1,2, -hisiallyloxymethyli 3.4.5.6-tetrachliiroben- Z6118 1A hisiallyloxymethyl) flfiflgfi-tetrmhlorobenzene sun further compounds ofthe invention, which contorm to the first general formula, when R" represents a bivalent, saturated, aliphatic hydrocarbon radical containing more than one carbon atom are of considerable interest. Among go such compounds there maybe mentioned the following:

1-pentachlorobenzyl-2-ethoxy ethane 1-pentachlorophenyl-3-methoxy propane 5 1-pentachlorophenyll-ethoxy butane 1-pentachlorophenyl-2-propoxy ethane 1,4-bis (betapropoxyethyl) -2,3;5,6-tetrachlorobenzene 35 contain either one or two halogenoalkyl or hydroxylaykyl groups attached to the benzene nucleus, the remaining hydrogens on the ring being substituted by chlorine. The halogenoalkyl groups preferably contain a single chlorine or bromine substituent which combines with the alkali-metal of the alcoholate in the first mentioned process.

The alcohols and aliphatic halides employed in the foregoing processes are preferably monovalent and may be either saturated or unsaturated.

Suitable alcohols for use in the first mentioned process include the methyl -ally1-, propyl-, 2- butenyl-, amyl-, pentenyl benzyl-, etc. alcohols. Aliphatic halides that may be employed in the 50 second process include the ethyl-, propenyl-,

butyl-, cinnamyl-, etc. chlorides and bromides.

In the following examples. given for purposes of illustration, the first mentioned process is used.

Obviously, in most cases the second process could 55 be substituted with substantially equivalent results.

3 EXAMPLE 1 Preparation of pentachlorobeneylchloride 1065 gms. of pentachlorotoluene were heated to its melting point, and chlorine was introduced, until the gain in weight was 137 gms. The crude reaction mixture was poured while hot into a distilling flask and fractionated at 0.27 mm. to yield a forerun, B. P. 120-132 C., weighing 70 gms. and the main fraction, B. P. 134-136" C.,' weighing 1063 gms. This main fraction melted at 72-95 C. Crystallization front a 50-50 ben-' zene-alcohol mixture gave 796 gms. melting at 99-102 0., representing a 66.5 chlorobenzylchloride.

EXAMPLE 2 Preparation of pentachlorobenzyl methyl ether A mixture of 14.9 gms. of pentachlorobenzylchloride, produced as described in Example 1, 10 gms. of sodium hydroxide and 100 cc. of methanol was refluxed for ten hours and then poured into water. The crude product was filtered and dried.

% yield of penta- It' weighed 14 gms. and melted at 97-110 C.

Crystallization from ethyl alcohol gave 9.5 gms.,

melting at 100-102 C. A sample crystallized for analysis two additional times from ethyl alcohol and once from acetone melted at 107.5-1085" C. Calculated for CsHOC15I C=32. 30%,H=1.70%. -Found by analysis? C=32.30 and 32.12%, H=1.49 and 1.79%.

. EXAMPLE 3 Preparation of pentachlorobenzyl ethyl ether A mixture of l4.9 gms. pentachlorobenzylchloride, produced asdescribed in Example 1, l0 gms.'of sodium hydroxide and 100 cc. ethanol was refluxed for two hours and water was then added. On cooling a solid precipitated. This was filtered and crystallized from 95% ethanol to yield 12 v gms. of the ether melting at 62-65 C. A sample crystallized for analysis four times from ethanol melted at 65-66 .C.-

Calculated for Cal-P100152 C=35.10%, H=2.29%. Found by analysis: (1:35.40 and 35.18%, H=2.12 and 1.98%.

EXAMPLE 4 Preparation of pen-tachlorobeney l prom/Z ether Sodium propoxide was prepared by adding 4.14 gms. sodium to 225 cc. n-propanol. 44.8 gms. pentachlorobenzylchloride, produced as described in Example 1, were added, and the mixture was refluxed for four hours and then poured into water. The organic material was extracted with chloroform. The chloroform extract was dried and distilled to yield 34 gms. (70%) of the desired ether, boiling at 131 C. at 0.4 mm. ing, the-ether crystallized, melting at 34-37" C. A sample crystallized for analysis four times from 95% ethanol melted at 43-44 C.

Calculated for CH9OC15:

Found by analysis: C=37.72 and 37.96%, H=3.01 and 2.78%..

EXAMPLE 5 Preparation of pentachlorophenyZ-n-butyl ether Sodium-n-butoxide was prepared by adding 13.8 gms. of sodium to 750 cc. n-butanol. 149.4 gms. or. pentachlorobenzylchloride, prepared as described in Example 1, were added, and the mixture was refluxed for twelve hours. Water was On stand-- then added. The butanol layer was separated, washed with saturated sodium chloride solution, dried over magnesium sulfate, filtered and distilled yielding 112 gms. of the ether, boiling at 138-139 C. at 0.4 mm. A small sample redistilled for analysis had a B. P. of 138-1395 C. at 0.3 mm. and a n of 1.5612. The ether is liquid 'at-room temperature.

Calculated for C11H11OC152 EXAMPLE 6 Preparation of 1,2-bis (bromomethyl) -3,4,5,6- tetrachlorobeneene Cl- CH Br Cl- OEzBr 244gms. of tetrachloro-ortho-xylene were dissolved in 750 cc. of carbon tetrachloride in a two liter flask equipped with a stirrer, reflux condenser and a dropping funnel, the flask being illuminated with an ultra-violet light. 320 gms. of

v bromine were added dropwise, until the bromine color disappeared. The solvent was evaporated off, leaving a crystalline-residue. This was recrystallized from an acetone-carbon tetrachloride mixture. The first crop amounted to 290 gms., M. P. 114-117" C. Three other crops yielded a total of 92 gms. with slightly lower melting points.

EXAMPLE 7 Preparation of 1,2-bis (n-proporymethyl) -3,4,5,6- tetrachlorobenzene 01- CHZO CH CH CH c1- CHzO 01110112033 201 gms. of the 1,2-bis(bromomethyl)-3,4,5,6- tetrachlorobenzene, produced as described in Example 6, were added to a solution of sodium n-propoxide made from 27.6 gms. of sodium and 750 cc. of n-propanol. The'mixture was refluxed over night, water added and the organic layer .1; separated and washed with saturated sodium chloride. The organic layer was then dried with magnesium sulfate and filtered. The excess propanol was distilled off at atmospheric pressure and the organic residue fractionated at reduced 20 gms. of 1,2-bis(bromomethyl)-3,4,5,6-tetra chlorobenzene, produced as described in Example 6 were added to a mixture of 27.6 gms. of potassium carbonate and cc. of allyl alcohol. The

mixture was refluxed with agitation for eight hours and then taken up in benzene. The solution was extracted with water, and the benzene layer dried over magnesium sulfate. The benzene was removed by distillation to leave an oil which did. not crystallize at room temperature. This oil Was fractionated to give 11.8 gins. of the product, B. P. 150-156 C. at 0.6 mm. The product was redistilled to obtain a sainple for analysis, B. 1?. 154 C. at .19 and ra of 1.5650.

Following the procedures outlined above, particularly that given in Example 3, it has been possible to produce ethers wherein the bivalent, saturated aliphatic hydrocarbon radical R, appearing in the first general formula hereinbefore given, is

and -CII2-CH2. Alpha-bromoethyl pentachlorobenzene may be refluxed with KOH and ethanol to give 1-pentach1orophenyl-l-ethoxyethane, M. P. 88-89 C. (Calculated for C10H9C15OZ c=37.2a%, H=2.79%. Found by analysis: :37.30 and 37.48%, H= .80 and 2.72%.) Betachloroethyl pentachlorobenzene may be refluxed with KOH and ethanol to give l-pentachlorophenyl-2-exthoxyethane, M. P. 8688 C. In each of these reactions, a large amount of pentachlorostyrene was obtained by dehydrohalogenation of the side chain.

The compounds of the invention are of utility in a wide variety of fields. Perhaps because chlorine and hydrogen atoms are not located on the same or adjacent carbon atoms, our new materials exhibit unusual chemical and electrical stability. The stability is particularly pronounced, when compared with chlorinated diphenyl oxide and other, known, halogenated aryl ethers.

Our new compounds are particularly desirable for electrical applications. They possess relatively high dielectric constants, due to their molecular structure. The boiling points are high, and the resistance to fiammation is exceptional. The butyl ether described in Example 5 and the bis-propoxymethyl compound described in Example are both liquid at room temperature, and are especiall suitable as liquid dielectric impregnants for electrical capacitors. The butyl ether possesses a dielectric constant in excess of 5 at 60 cycles A. C. V

The high chlorine content of th compounds results in their applicability where resistance to flame is a determining factor. The compounds and mixtures thereof are useful as heat-transfer mediums, as modifiers for increasing the flash point of oils, finishes and the like, as transformer fluids and, for certain applications, as lubricating mediums.

The polar nature and other features of the compounds described herein permit their use as plasticizers for resinous materials. The polyvinylhalides in particular may be modified by incorporation therewith of the halo ethers of the invention. The chlorine content of our ethers results in satisfactory compatibility, and the flame resistance of the resin may be increased by such modification.

The diallyl di-ether described in Example 8 is capable of polymerization per se and of copolyrfiBTlZZvttiOl'l with other polymerizable materials, such as styrene, halogenated styrenes, etc. For this reason, it and its related compounds are desirable materials to be used to modify the properties of normally polymerized resins. It can be used in place of such compounds as dioctyl phthal-ate and diallyl phthalate, to increase flame resistance of resinous materials used for paints, coatings and the like. If so desired, the diallyl di-ether may be added to the resin and copolymerized therewith. A sample of 1,2-bis (allyloxymethyl)3,4,5,6-tetrachlorobenzene polymerized to a soft resin state, when held at 165 C. for hours in the presence of benzoyl peroxide. A mixture of two parts of pentachlorostyrene and one part of the above diallyl compound co-polymerized to form a. hard resin, when held at 165 C. for 90 hours in the presence of 3% benzoyl peroxide. The resin was somewhat softer than polypentachlorostyrene.

It is contemplated that the monovalent, aliphatic hydrocarbon radical R in the first two general formulae may be further substituted for special applications, for example, where lectrical stability is not an important factor.

As many widely different embodiments of this invention may be made without departing from the spirit and scope hereof, it is to be understood that the invention is not limited to the specific embodiments hereof except as defined in the appended claim.

What we claim is:

1,2, bis(allyloxymethyl) 3,4,5,6 tetrachlorobenzene.

SIDNEY D. ROSS. MOUSHY MARKARIAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,072,797 Clark Mar. 2, 1937 2,073,010 Holt Mar. 9, 1937 FOREIGN PATENTS Number Country Date 551,832 Great Britain Mar. 11, 1943 Certificate of Correction Patent No. 2,564,214 August 14, 1951 SIDNEY D. ROSS ET AL.

It is hereby certified that error-appears in the printed specification of the above numbered patent requiringj correction as follows: 9

Column 2, line 23, for 1-pentach1orobenzyl-2-ethoxy ethane read l-pentaohlorophenyZ-2-ethowy ethane; line 29, for compound read compounds; column 5, line 27, for exthoxyethane read ethowyethane;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the ease in the Patent Oflioe.

Signed and sealed this 23rd day of October, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

